Acid anhydride modified acrylate monomer as well as preparation method and application thereof

Abstract

The invention discloses an acid anhydride modified acrylate monomer as well as a preparation method and application thereof. The structural formula of the acid anhydride modified acrylate monomer is shown as a formula (I), the acid anhydride modified acrylate monomer provided by the invention has good adhesive force and weather resistance as well as excellent water resistance and high temperature resistance, and is expected to be well applied to the fields of coatings and printing ink.

Description

Technical Field

[0001] This invention belongs to the field of photosensitive polymer materials technology, and particularly relates to an anhydride-modified acrylate monomer, its preparation method and application. Background Technology

[0002] The traditional coatings industry has long faced challenges such as environmental pollution, resource waste, and performance limitations. Traditional coatings rely on organic solvents for dilution, resulting in significant emissions of volatile organic compounds (VOCs), posing a threat to the environment and human health. Furthermore, traditional coatings are difficult to degrade, leading to resource waste and environmental pollution upon disposal. In terms of performance, traditional coatings have limitations in water resistance and high-temperature resistance, failing to meet the growing application demands. Therefore, providing a monomer for preparing coatings that are less environmentally polluting, water-resistant, and high-temperature resistant is an urgent problem to be solved. Summary of the Invention

[0003] To address the shortcomings of the prior art, this invention provides an anhydride-modified acrylate monomer, which exhibits good adhesion, weather resistance, and excellent water resistance and high-temperature resistance, and is expected to achieve good applications in the fields of coatings and inks.

[0004] The purpose of this invention is to provide an anhydride-modified acrylate monomer, the structural formula of which is shown in formula (I):

[0005] Equation (Ⅰ);

[0006] Where R is , , , , or .

[0007] In some embodiments of the present invention, R is , , or .

[0008] Another object of the present invention is to provide a method for preparing the anhydride-modified acrylate monomer, comprising the following steps:

[0009] S1. Mix an acid anhydride compound, glucose, a first catalyst, and a first solvent, and heat to react to obtain an acid anhydride-modified glucose;

[0010] S2. Under an inert gas atmosphere, the anhydride-modified glucose, acrylic acid, a second catalyst, a polymerization inhibitor, and a second solvent are mixed and heated to react, thereby obtaining the anhydride-modified acrylate monomer.

[0011] In some embodiments of the present invention, in S1, the acid anhydride compound is selected from at least one of succinic anhydride, maleic anhydride, dimethylmaleic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, and phthalic anhydride.

[0012] In some embodiments of the present invention, in S1, the first catalyst is selected from at least one of pyridine, triethylamine, and p-toluenesulfonic acid.

[0013] In some embodiments of the present invention, in S1, the first solvent is selected from a mixture of solvent A and solvent B, wherein solvent A is selected from at least one of DMF and DMSO, and solvent B is selected from at least one of cyclohexane and toluene.

[0014] In some embodiments of the present invention, in S1, the molar ratio of the acid anhydride compound to glucose is 1:2.05~2.15.

[0015] In some embodiments of the present invention, in S1, the amount of the first catalyst is 5 to 15% of the amount of glucose.

[0016] In some embodiments of the present invention, in S1, the amount of the first solvent is 300 to 800% of the total mass of the reaction substrate.

[0017] In some embodiments of the present invention, in S1, the temperature of the heating reaction is 70~110°C and the time is 2~6 hours.

[0018] In some embodiments of the present invention, in step S2, the inert gas is at least one of nitrogen and argon.

[0019] In some embodiments of the present invention, in S2, the second catalyst is selected from at least one of triphenylphosphine, tetrabutylammonium bromide, p-toluenesulfonic acid, zinc oxide, and Pd catalyst.

[0020] In some embodiments of the present invention, in S2, the polymerization inhibitor is selected from at least one of hydroquinone, tert-butylhydroquinone, phenothiazine, p-hydroxyanisole, and 2-tert-butylhydroquinone.

[0021] In some embodiments of the present invention, in S2, the second solvent is selected from at least one of cyclohexane and toluene.

[0022] In some embodiments of the present invention, in S2, the molar ratio of acrylic acid to anhydride-modified glucose is 6.05~6.2:1.

[0023] In some embodiments of the present invention, in S2, the amount of the polymerization inhibitor is 1000~4000 ppm of the total mass of the reaction substrate.

[0024] In some embodiments of the present invention, in S2, the amount of the second catalyst is 800 to 2500 ppm of the total mass of the reaction substrate.

[0025] In some embodiments of the present invention, in S2, the amount of the second solvent is 30 to 200% of the total mass of the reaction substrate.

[0026] In some embodiments of the present invention, in S2, the temperature of the heating reaction is 50~130°C and the time is 3~8 hours.

[0027] Another object of the present invention is to provide the application of the anhydride-modified acrylate monomer or the anhydride-modified acrylate monomer prepared by the preparation method of the anhydride-modified acrylate monomer in the preparation of coatings and inks.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] This invention uses bio-based monomer glucose as a raw material to react and obtain multifunctional anhydride-modified acrylate monomers, which are then added to a UV curing system. This results in a coating with high crosslinking density, good curing rate, excellent adhesion and weather resistance, and strong water and high temperature resistance. It avoids the shortcomings of low crosslinking density, poor curing film stability, and poor adhesion in the prepared coating, and is expected to achieve good applications in the fields of coatings and inks. Detailed Implementation

[0030] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0031] DPHA: Dipentaerythritol hexaacrylate, an acrylic monomer purchased from Changxing Materials Industry Co., Ltd.

[0032] Photoinitiator 1173: 1-hydroxy-1-methylethylphenyl ketone, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0033] Vinyl ester resin: Yueteng-901, a conventional commercially available general-purpose bisphenol A epoxy vinyl resin.

[0034] Example 1

[0035] This embodiment provides an anhydride-modified acrylate monomer M1, the preparation method of which includes the following steps:

[0036] S1. Add (10 g, 0.10 mol) succinic anhydride, (37.8 g, 0.21 mol) glucose, (1.89 g, 0.011 mol) p-toluenesulfonic acid, (50 g) cyclohexane and (100 g) DMF to a 250 ml four-necked flask. Install a stirrer and a reflux device, and slowly heat to 50°C while stirring to ensure the system is mixed evenly. Then raise the temperature to 100°C ± 2°C and keep the temperature for 3 hours. During this period, observe the total amount of water produced in the system. When the amount of water produced is close to the theoretical amount and no water is generated in the reflux solvent, the reaction is considered to be over. Stop the reaction, slowly add the reactants dropwise into a vigorously stirred aqueous solution, filter the precipitate, and dry it under vacuum to obtain anhydride-modified glucose.

[0037] S2. The above-mentioned (27.22 g, 0.1 mol) anhydride-modified glucose, (43.92 g, 0.61 mol) acrylic acid, (0.21 g, 3000 ppm) p-hydroxyanisole, (0.07 g, 1000 ppm) p-toluenesulfonic acid, (80 g) cyclohexane, and (60 g) toluene were successively added to a 250 ml four-necked flask. A stirring device was installed and nitrogen gas was introduced. The mixture was slowly heated to 60°C and stirred until the solid-dissolved system was homogeneous. Then, the temperature was raised to 90°C ± 2°C and the reaction was maintained for 4 hours. The acid value was titrated until it no longer changed, and then the reaction was stopped. Excess acrylic acid compound was removed with sodium hydroxide solution, and then dried with anhydrous magnesium sulfate and the solvent was removed by vacuum distillation to obtain anhydride-modified acrylate monomer M1 with an acid value <0.2 mgKOH / g (test standard: GB / T6743-2008) and a viscosity of 8000 cps at 25°C (test standard: GB / T (2794-2013), solid content 97% (baked at 110℃); the structure of the anhydride-modified acrylate monomer M1 is as follows:

[0038] ;

[0039] The 1H NMR spectrum of the anhydride-modified acrylate monomer M1 is as follows:

[0040] 1 H NMR(400 MHz, CDCl3, ppm): δ 7.36(d, 2H, CH), 6.42(d, 6H, CH2), 6.10(d, 6H, CH), 5.97(d, 2H, CH), 5.82(d, 6H, CH2), 5.34(d, 2H, CH), 4.89(s, 2H,OH), 4.32-4.19(m, 8H, CH and CH2), 2.74(s, 4H, CH2).

[0041] Example 2

[0042] This embodiment provides an anhydride-modified acrylate monomer M2, the preparation method of which includes the following steps:

[0043] S1. Add (9.8 g, 0.10 mol) maleic anhydride, (37.8 g, 0.21 mol) glucose, (1.89 g, 0.011 mol) p-toluenesulfonic acid, (50 g) cyclohexane and (100 g) DMF to a 250 ml four-necked flask. Install a stirrer and a reflux device, and slowly heat to 50°C while stirring to ensure the system is mixed evenly. Then raise the temperature to 100°C ± 2°C and keep the temperature for 3 hours. During this period, observe the total amount of water produced in the system. When the amount of water produced is close to the theoretical amount and no water is generated in the reflux solvent, the reaction is considered to be over. Stop the reaction, slowly add the reactants dropwise into a vigorously stirred aqueous solution, filter the precipitate, and dry it under vacuum to obtain anhydride-modified glucose.

[0044] S2. The above-mentioned (25.22 g, 0.1 mol) anhydride-modified glucose, (43.92 g, 0.61 mol) acrylic acid, (0.21 g, 3000 ppm) p-hydroxyanisole, (0.07 g, 1000 ppm) p-toluenesulfonic acid, (80 g) cyclohexane, and (60 g) toluene were successively added to a 250 ml four-necked flask. A stirring device was installed and nitrogen gas was introduced. The mixture was slowly heated to 60°C and stirred until the solid-dissolved system was homogeneous. Then, the temperature was raised to 90°C ± 2°C and the reaction was maintained for 4 hours. The acid value was titrated until it no longer changed, and then the reaction was stopped. Excess acrylic acid compound was removed with sodium hydroxide solution, and then dried with anhydrous magnesium sulfate and the solvent was removed by vacuum distillation to obtain anhydride-modified acrylate monomer M2 with an acid value <0.2 mgKOH / g (test standard: GB / T6743-2008) and a viscosity of 8100 cps at 25°C (test standard: GB / T (2794-2013), solid content 96% (baked at 110℃); the structure of the anhydride-modified acrylate monomer M2 is as follows:

[0045] ;

[0046] The 1H NMR spectrum of the anhydride-modified acrylate monomer M2 is as follows:

[0047] 1H NMR(400 MHz, CDCl3, ppm): δ 7.37(d, 2H, CH), 6.43(d, 8H, CH andCH2), 6.14(d, 6H, CH), 5.94(d, 2H, CH), 5.84(d, 6H, CH2), 5.35(d, 2H, CH),4.87(s, 2H, OH), 4.38-4.19(m, 8H, CH and CH2).

[0048] Example 3

[0049] This embodiment provides an anhydride-modified acrylate monomer M3, the preparation method of which includes the following steps:

[0050] S1. Add (16.6 g, 0.10 mol) methyltetrahydrophthalic anhydride, (37.8 g, 0.21 mol) glucose, (1.89 g, 0.011 mol) p-toluenesulfonic acid, (50 g) cyclohexane and (100 g) DMF to a 250 ml four-necked flask. Install a stirrer and a reflux device, and slowly heat to 50°C while stirring to ensure uniform mixing. Then raise the temperature to 100°C ± 2°C and maintain the temperature for 3 hours. During this period, observe the total amount of water produced in the system. When the amount of water produced is close to the theoretical amount and no water is generated in the reflux solvent, the reaction is considered complete. Stop the reaction and slowly add the reactants dropwise into a vigorously stirred aqueous solution. Filter the precipitate and dry it under vacuum to obtain anhydride-modified glucose.

[0051] S2. The above-mentioned (32.83 g, 0.1 mol) anhydride-modified glucose, (43.92 g, 0.61 mol) acrylic acid, (0.23 g, 3000 ppm) p-hydroxyanisole, (0.08 g, 1000 ppm) p-toluenesulfonic acid, (100 g) cyclohexane, and (50 g) toluene were successively added to a 5000 ml four-necked flask. A stirring device was installed and nitrogen gas was introduced. The mixture was slowly heated to 60°C and stirred until the solid-dissolved system was homogeneous. Then, the temperature was raised to 90°C ± 2°C and the reaction was maintained for 4 hours. The acid value was titrated until it no longer changed, and then the reaction was stopped. Excess acrylic acid compound was removed with sodium hydroxide solution, and then dried with anhydrous magnesium sulfate and the solvent was removed by vacuum distillation to obtain anhydride-modified acrylate monomer M3 with an acid value <0.2 mgKOH / g (test standard: GB / T6743-2008) and a viscosity of 8600 cps at 25°C (test standard: GB / T (2794-2013), solid content 97% (baked at 110℃); the structure of the anhydride-modified acrylate monomer M3 is as follows:

[0052] ;

[0053] The 1H NMR spectrum of the anhydride-modified acrylate monomer M3 is as follows:

[0054] 1 H NMR(400 MHz, CDCl3, ppm): δ 7.37(d, 2H, CH), 6.77(s, 1H, CH), 6.40(d, 6H, CH2), 6.13(d, 6H, CH), 5.95(d, 2H, CH), 5.80(d, 6H, CH2), 5.35(d, 2H,CH), 4.87(s, 2H, OH), 4.37-4.06(m, 8H, CH and CH2), 2.60-2.07(m, 6H, CH2), 1.40(s, 3H, CH3).

[0055] Example 4

[0056] This embodiment provides an anhydride-modified acrylate monomer M4, the preparation method of which includes the following steps:

[0057] S1. Add (14.8 g, 0.10 mol) phthalic anhydride, (37.8 g, 0.21 mol) glucose, (1.89 g, 0.011 mol) p-toluenesulfonic acid, (50 g) cyclohexane and (100 g) DMF to a 250 ml four-necked flask. Install a stirrer and a reflux device, and slowly heat to 50°C while stirring to ensure the system is mixed evenly. Then raise the temperature to 100°C ± 2°C and keep the temperature for 3 hours. During this period, observe the total amount of water produced in the system. When the amount of water produced is close to the theoretical amount and no water is generated in the reflux solvent, the reaction is considered to be over. Stop the reaction, slowly add the reactants dropwise into a vigorously stirred aqueous solution, filter the precipitate, and dry it under vacuum to obtain anhydride-modified glucose.

[0058] S2. The above-mentioned (31.03 g, 0.1 mol) anhydride-modified glucose, (43.92 g, 0.61 mol) acrylic acid, (0.22 g, 3000 ppm) p-hydroxyanisole, (0.07 g, 1000 ppm) p-toluenesulfonic acid, (100 g) cyclohexane, and (50 g) toluene were successively added to a 5000 ml four-necked flask. A stirring device was installed and nitrogen gas was introduced. The mixture was slowly heated to 60°C and stirred until the solid-dissolved system was homogeneous. Then, the temperature was raised to 90°C ± 2°C and the reaction was maintained for 4 hours. The acid value was titrated until it no longer changed, and then the reaction was stopped. Excess acrylic acid compound was removed with sodium hydroxide solution, and then dried with anhydrous magnesium sulfate and the solvent was removed by vacuum distillation to obtain anhydride-modified acrylate monomer M4 with an acid value <0.2 mgKOH / g (test standard: GB / T6743-2008) and a viscosity of 8400 cps at 25°C (test standard: GB / T (2794-2013), solid content 98% (baked at 110℃); the structure of the anhydride-modified acrylate monomer M4 is as follows:

[0059] ;

[0060] The 1H NMR spectrum of the anhydride-modified acrylate monomer M4 is as follows:

[0061] 1 H NMR(400 MHz, CDCl3, ppm): δ 8.04(d, 2H, Ph), 7.70(d, 2H, Ph), 7.38(d, 2H, CH), 6.44(d, 6H, CH and CH2), 6.11(d, 6H, CH), 5.92(d, 2H, CH), 5.80(d, 6H, CH2), 5.33(d, 2H, CH), 4.86(s, 2H, OH), 4.50-4.19(m, 8H, CH and CH2).

[0062] Example 5

[0063] This embodiment provides a coating, the preparation method of which includes the following steps:

[0064] Weigh out 8 g of vinyl ester resin, 2 g of anhydride-modified acrylate monomer M1, and 0.3 g of photoinitiator 1173, mix them, and stir evenly in a 65°C water bath to remove air bubbles. Apply the coating to a PC board using a 12 μm thick wire rod. After standing for 5 minutes, cure under mercury lamp radiation for 10 seconds at a radiation intensity of 250 mJ·cm. -2 This results in a fully cured coating.

[0065] Example 6

[0066] This embodiment provides a coating, the preparation method of which includes the following steps:

[0067] The anhydride-modified acrylate monomer M1 in Example 5 was replaced with anhydride-modified acrylate monomer M2, and the remaining steps were the same as in Example 5, to obtain the coating.

[0068] Example 7

[0069] This embodiment provides a coating, the preparation method of which includes the following steps:

[0070] The anhydride-modified acrylate monomer M1 in Example 5 was replaced with anhydride-modified acrylate monomer M3, and the remaining steps were the same as in Example 5, to obtain the coating.

[0071] Example 8

[0072] This embodiment provides a coating, the preparation method of which includes the following steps:

[0073] The anhydride-modified acrylate monomer M1 in Example 5 was replaced with anhydride-modified acrylate monomer M4, and the remaining steps were the same as in Example 5, to obtain the coating.

[0074] Comparative Example 1

[0075] This comparative example provides a coating whose preparation method includes the following steps:

[0076] The anhydride-modified acrylate monomer M1 in Example 5 was replaced with the acrylate monomer DPHA, and the remaining steps were the same as in Example 5, to obtain the coating.

[0077] Glass transition temperature (Tg) test: The instrument mainly used is a Netzsch DSC3500 differential scanning calorimeter, with a test temperature range of 25℃~300℃. Specific requirements can be found in GB / T 19466.2-2004 standard. Generally, for coatings, the higher the crosslinking density, the higher the glass transition temperature.

[0078] Chemical solvent resistance test: The PC boards with the cured film were immersed in deionized water, 0.05 mol / L hydrochloric acid solution, 0.05 mol / L sodium hydroxide solution, and anhydrous ethanol, respectively, and placed in an oven at 25°C for 12 hours. The coating was observed to see if it showed signs of loss of gloss, swelling, discoloration, peeling, or spots. If no such phenomena were observed, it indicated that the coating was intact and had good chemical solvent resistance, represented by 0. If signs of loss of gloss, swelling, discoloration, peeling, or spots were observed, it indicated that the coating was damaged, represented by Roman numerals 1-5, with larger numbers indicating more severe damage.

[0079] Adhesion Test: The adhesion of the coating on the PC board is determined using the cross-cut test. One hundred 1 mm × 1 mm squares are drawn on the coating surface using a paint film scratch tester. 3M tape is then applied to the coating and pressed firmly. Finally, the tape is peeled off the coating surface at a 180° angle. The coating surface condition is observed to see if the coating is completely peeled off, if the squares are peeled off, or if the coating remains intact. The adhesion grade is 0-5B, generally requiring an adhesion grade greater than or equal to 3B. Specific procedures can be performed according to GB / T 9286-1998 standard.

[0080] Water boiling resistance test: The coating attached to the PC board is immersed in a water bath at 90°C. After boiling for different times, the adhesion of the coating on the PC board is measured by cross-cut test.

[0081] Table 1. Coating performance test results of Examples 5-8 and Comparative Example 1.

[0082]

[0083] As shown in Table 1, the anhydride-modified acrylate monomers M1 to M5 of the present invention are used to prepare coatings. The resulting coatings have high glass transition temperature, good chemical solvent resistance, strong adhesion, and good high temperature resistance.

[0084] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that after reading this application specification, they can still modify or make equivalent substitutions to the specific implementation of the present invention, but these modifications or changes do not depart from the protection scope of the pending claims of the present invention.

Claims

1. An anhydride-modified acrylate monomer, characterized in that, The structural formula of the anhydride-modified acrylate monomer is shown in Formula (Ⅰ): Equation (Ⅰ); Where R is , , , , or .

2. The anhydride-modified acrylate monomer according to claim 1, characterized in that, The R is , , or .

3. The method for preparing anhydride-modified acrylate monomers according to any one of claims 1 to 2, characterized in that, Includes the following steps: S1. Mix an acid anhydride compound, glucose, a first catalyst, and a first solvent, and heat to react to obtain an acid anhydride-modified glucose; S2. Under an inert gas atmosphere, the anhydride-modified glucose, acrylic acid, a second catalyst, a polymerization inhibitor, and a second solvent are mixed and heated to react, thereby obtaining the anhydride-modified acrylate monomer.

4. The method for preparing anhydride-modified acrylate monomers according to claim 3, characterized in that, In S1, the acid anhydride compound is selected from at least one of succinic anhydride, maleic anhydride, dimethylmaleic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, and phthalic anhydride. And / or, the first catalyst is selected from at least one of pyridine, triethylamine, and p-toluenesulfonic acid; And / or, the first solvent is selected from a mixture of solvent A and solvent B, wherein solvent A is selected from at least one of DMF and DMSO, and solvent B is selected from at least one of cyclohexane and toluene.

5. The method for preparing anhydride-modified acrylate monomers according to claim 3, characterized in that, In S1, the molar ratio of the acid anhydride compound to glucose is 1:2.05~2.15; And / or, the amount of the first catalyst is 5-15% of the amount of glucose; And / or, the amount of the first solvent is 300 to 800% of the total mass of the reaction substrate.

6. The method for preparing anhydride-modified acrylate monomers according to claim 3, characterized in that, In S1, the heating reaction is carried out at a temperature of 70~110℃ for 2~6 hours.

7. The method for preparing anhydride-modified acrylate monomers according to claim 3, characterized in that, In S2, the inert gas is at least one of nitrogen and argon; And / or, the second catalyst is selected from at least one of triphenylphosphine, tetrabutylammonium bromide, p-toluenesulfonic acid, zinc oxide, and Pd catalyst; And / or, the polymerization inhibitor is selected from at least one of hydroquinone, tert-butylhydroquinone, phenothiazine, p-hydroxyanisole, and 2-tert-butylhydroquinone; And / or, the second solvent is selected from at least one of cyclohexane and toluene.

8. The method for preparing anhydride-modified acrylate monomers according to claim 3, characterized in that, In S2, the molar ratio of acrylic acid to anhydride-modified glucose is 6.05~6.2:1; And / or, the amount of the polymerization inhibitor is 1000~4000 ppm of the total mass of the reaction substrate; And / or, the amount of the second catalyst is 800 to 2500 ppm of the total mass of the reaction substrate; And / or, the amount of the second solvent is 30 to 200% of the total mass of the reaction substrate.

9. The method for preparing anhydride-modified acrylate monomers according to claim 3, characterized in that, In S2, the heating reaction is carried out at a temperature of 50~130℃ for 3~8 hours.

10. The application of anhydride-modified acrylate monomers prepared by the method of preparing anhydride-modified acrylate monomers according to any one of claims 1 to 2 or according to any one of claims 3 to 9 in the preparation of coatings and inks.

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